New azo dyestuffs and a process for dyeing polyacrylic fibres



NEW AZO DYESTUFFS- AND A PRGCESS FQR DYEING POLYACRYLIC FIERES Robert Frdric Michel Sureau, Enghien-les-Bains, and

Gilbert Krmer, Ermont, France, assignors to Compagnie Francaise des Matieres Colorantes, Paris,

France, a French company No Drawing. Filed May 5, 1961, Ser. No. 107,888 Claims priority, application France May 6, 1960 6 (Ilaims. (Cl. 8-41) The present invention relates to the application to the colouration of polyacrylic fibres of amino-monoazo dyestuffs of the general formula:

NHz

in which X represents a hydrogen or chlorine atom, Y represents a methyl or ethyl group and Z represents a phenyl group which may be substituted by chlorine atoms,

methyl groups, methoxy groups, ethoxy groups, nitro groups, trifluoromethyl groups, or dimethylamino groups. It has been found that the dyestufis of Formula I in the form of salts soluble in water are capable of colouring synthetic fibres based on polymers or copolymers of acrylonitrile.

These dyestuffs are generally very soluble in the form of salts of mineral acids or strong organic acids such as, for example, hydrochloric acid, sulphuric acid, formic acid or chloracetic acids. They dye fibres based on polymers or copolymers of acrylonitrile in shades, passing from orange yellow to violet, which are generally very brilliant and which have good general fastness. The dyeing is carried out at the boil in the presence of a small quantity, e.g., 1% to 2% based on the weight of the fibre, of mineral or strong organic acid.

Dyestufis of Formula I may be obtained, for example, by means of either of the following processes:

A. Diazotisation of a primary benzenic amine and coupling with a 6arnino-2-alkyl-indazole of the general formula:

lTlHa B. Diazotisation of a primary benzenic amine, coupling I with a o-amino-indazole of the formula:

in which X has the meaning given above. Treatment of the dyestuff thus obtained with methyl or ethyl halide or arenas? Patented Dec. 8, 1964 sulphate in an organic solvent medium results in a water soluble salt. It has been found, in fact, that the action ofthese alkylating agents is shown by fixation of an alkyl group in the 2-position and precipitation of the alkylated dyestufi; the latter is converted into the salt by the anion liberated during the alkylation. On account of the insolubility of the salt of the dyestufi thus obtained in the reaction medium, the reaction stops at this stage. The

saline non-quaternary nature of the dyestuff obtained is easily shown thus: on making its aqueous solution alkaline, a dyestufi identical with that obtained by the first method is liberated.

The following examples are given without the invention being limited thereto; the parts are by weight unless the contrary is indicated.

Example 1 24 parts of p-anisidine are dissolved in 200 parts of water and 60 parts by volume of hydrochloric acid at a. concentration of 365 g. per litre. Ice is added to keep the temperature between 0C. and 5 C. and diazotisation is effected by the addition of 14 parts of sodium nitrite dissolved in '25 parts of water. After 20 minutes, any excess of nitrous acid is destroyed by the addition of just sufiicient sulphamic acid solution, the reaction product is filtered and the diazo derivative is introduced into a solution of 28 parts of 6-amino-indazole in 400 parts of water and 22 parts by volume of hydro chloric acid at a concentration of 365 g. per litre. About 200 parts by volume of a 25% solution of sodium acetate are slowly added until a neutral reaction is given with Congo red paper. coupling is finished by the slow introduction of dilute ammonia so as to bring the pH to 6 to 6.5. After mixing for an hour, the medium is made distinctly alkaline by a fresh addition of ammonia. The free base of the dye- I polyacrylic fibres in a boiling neutral bath or a bath slightly acid with sulphuric acid, e.g., containing 1% to 2% of acid based on the weight of the fibres, and gives a full-bodied red shade which is a little more bluish than that of the dyestufr" not treated with dimethyl sulphate;

Example 2 I 14 parts of the dyestufi obtained in a similar way to that of Example 1, by coupling the diazo derivative ofp-phenetidine with 6-amino-indazole, are dissolved in 300' parts of boiling chlorobenzene. The filtered solution is treated with a mixture of 15 parts of diethyl sulphate and 60 parts of chlorobenzene over a period of l5mi'nutes under gentle reflux, and gentle boiling is continued for 2 hours. The product is allowed to cool, the solvent is separated and the tarry sediment is taken up: with two lots of 300 parts of boiling water. ,The solution obtained is filtered in order to separate an insoluble'residue and 250 parts by volume of a saturated solution ofsodium chloride are added to the filtrate at'50 to 60'v C.

The mixture isallowed to cool with stirring and the dark red brown precipitate obtained is filtered off. The dyestufi dyes polyacrylic fibres a Bordeaux shadehaving ex- 7 cellent general fastnessp, j I I Exantpled 24 parts of p-anisidine are dissolved in .200 parts of water and 60 parts by volume ofhydrochloric acid at After stirring for two hours, the

a concentration of 365 g. per litre. Ice is added to keep the temperature between C. and 5 C. and diazotisation is eifected by the addition of 14 parts of sodium nitrite dissolved in parts of water. 'After 20 minutes any excess nitrous acid present is. destroyed by" the. addition of just sufiicient sulphamic acid solution, the, product is filtered and the diazoderivan've. thus; obtained is. introduced into a solution of parts of G-amino-Z-meth-ylindazole in 400parts: of water and 22:par.ts-. by volume of hydrochloric acid at a concentration of 3.65; g. per litre. About 200 partsv by. volume ofa 25% solution. of sodium acetate are slowly addedauntili aneutral reaction on Congo red paper is obtained; After stirring-for. two hours, thecoupling is finished by thexslow-introdudtion of a dilute solution of ammonia so as. to bringthe; pH to 6 to 6.5. After stirring for an hour, the precipitated aminoazo compound is filtered off, washed; and dried at 100 C. partsof dyestufl are thus obtained in the form of the dark red brown. hydrochloride.

This dyestuff dyes fibres, based on polymers or c0- polymers of acrylonitrile from a bath containing 1% of sulphuric or monochloracetic acid; calculated on the weight of the material, a full-bodied bright red shade having very good general fastness.

If an aqueous solution of' this dyestuffr made dis: tinctly alkaline by the addition of: caustic soda, the dyestufi is precipitated asthe free base, the melting-point of which is- 18 5 to 186 C. after recrystallisation from chlorobenzene.

If, on the other hand, the same process of rendering alkaline is carried out on a solution of the; dy'estufiobtained according to Example 1 by the action of methyl sulphate on the aminoa zo compound resulting. from coupling the diazo derivative of 'p-anisidine with 6-amino,- indazole, a dyestuff identical with the above is obtained, of melting point 185 to 186 C., which isnot lowered on mixing the two.

In the following table a number of other analogous. ex-v amples are grouped together.

. I 4 We claim; 1. A process for colouring polyacrylic fibres which comprises dyeing the fibres with'a Water-soluble salt of a dyestuff selected from the group consisting of the dyestuffs of the general formula:

in which X represents a member selected from the group. consisting of the hydrogen and chlorine atoms, Y represents a member selected from the group consisting of the I Shade on poly- 1 acrylic fibresof No. Diazotised amine Amine coupled the dyestutl treated with dimethyl sulphateo-Ohloraniline G-amino-indazole. Red orange. m-Ohloraniline. dQ Orange. o-Anisidine- Bluish red. o-Tolui dine Scarlet. m-Toluidine Orange. p-Toluidine- Red orange. o-Nitraniline Orange. m-Nitraniline Do. mrifiuoromethyl- Do. aniline.

p-Dimethylamino- Green grey.

aniline. o-Phenetidine. Red. p-Phenetidine. Bhn'sh red. 2,4-dimethylaniline- Scarlet.

4-Oh1oro-2-amino- Reddishorange.

toluene. 1 V 4-Nitro-2-amino-anisole lo Orange. 3-Nitro4-amin0-anisole" do Bordeaux. -Ohloro-Z-arninodo Red.

anisole. a 2, 5- dimethoxyauiline Violet. 4-Methyl-2 amino- Bordeaux.

anisole. Anilinedarnino-S-chloro- Orange.

. indazole d Do. Do. Red. p-Anisidine Bluish red. p-Nitraniline Orange.

the dyestuif of the'following formula:

methyl and ethyl groups, and. Z represents a member se lected from the groups consisting of the unsubstituted phenyl group and phenyl groups substituted by members selected from the group consisting of the chlorine atom, the methyl group, the methoxy group, the ethoxy group, the nitro group, the trifluoromethyl group, the dimethylamino group, the dyeing taking place at the boil in the presence of a member selected'from the group. consisting} of mineral andstrong organic acids.

2. A process for] colouring, polyacr'yl-ic fibresv which comprises dyeing the. fibres. with a water-soluble salt of the dyestutf of'the following formula:

( on. 17TH;

a N s...

the dyeing taking place. at the boil in, thev presence of a member selected from the group. consisting of; mineral and strong organic acids.

3. A process for colouring poly-acrylic fibres which comprises: dyeing the fibres with a water-soluble salt of; the dyestufi'of the following formula: 1

the dyeing taking place at the boil in the presence of a member selected from" the group .consistingzof mineral and strong organic acids.

4. A process for colouring comprises dyeing the fibres with a Water-soluble polyacrylic fibres which sait of the dyeing taking place at the boil in the presence of a member selected from the group consisting of mineral and strong organic acids.

5. A process for colouring polyacrylic fibres which comprises dyeing the fibres with a water-soluble salt of the dyestuif of the following formula:

CH3 I NH: O O

l O C H; N C H the dyeing taking place at the boil in the presence of a member selected from the group consisting of mineral and strong organic acids.

References Cited in the file of this patent UNITED STATES PATENTS 2,282,323 Dickey et a1 May 12, 1942 2,308,023 Peterson et a1 Jan. 12, 1943 2,819,943 Rhyner et al. Ian. 14, 1958 2,825,726 Towne et al. Mar. 4, 1958 2,828,301 Sureau et al Mar. 25, 1958 2,857,371 Straley et a1 Oct. 21, 1958 2,868,775 Straley et a1 Jan. 13, 1959 2,883,373 Bossard et a1 Apr. 21, 1959 2,889,315 Bossard et a1 June 2, 1959 

1. A PROCESS FOR COLOURING POLYACRYLIC FIBRES WHICH COMPRISES DYEING THE FIBRES WITH A WATER-SOLUBLE SALT OF A DYESTUFF SELECTED FROM THE GROUP CONSISTING OF THE DYESTUFFS OF THE GENERAL FORMULA: 